Horticultural composition comprising polyethylene polysulfide and sulfur or lime-sulfur



. provides forgcohvenientfmixing"and applyin oil" Patented Sept. 18,1951 Ysfr A'r PA No Drawing- Am lication April 1947- 2:.

. s ri No. 740,968

- "commas. (01.167-20) This invention relates to horticultural spraysulphur or lime-sulphur with'an aqueous dispercompositions; and jlllbre"specificallyfpertains to sion of a polymeric organic polysuifldeespesynergistic spray adjuvants ior sulphur and limecially those aqueousof polymeric sulphur spray compositions. organic polysulfidesiwhichhrecapable of'micro j Sulphur andlime-sulphurarerwidely used in 5 seep1e,easement;oiseentmueuszjiubperymms the agricultural andp horticulturalindustries for uondr'ying; flhesef pre ferredaqueous dispersionsinsecticidal and fungicidal purposes. Elemental of polymericorganicpolysulfldesare more com sulphur in its many modiiiedformscan beused pletely heremarte" defined' 'fi Q as a dust or can be dispersed inan aqueous The polymericjorganici polysulildeswhichare medium and usedas both a fungicide and an preferred for thefpurposes oi inyention'areinsecticide. Lime-sulphurisalmost entirely emthose which haveltheformula "for the 1 ployed either as an aqueoussolution freshlyprestr'u ural molecular oi '+Rf-S="l where pared by the reaction of anaqueous suspension R isan"Qrg nie \radi a1"h vmg m5 sulphurafloofcalcium hydroxide with some form of elemental suiphur linka e, ialidjrt'jot Se a value of from sulphur or as a'commercially availableaqueous 2 tos ormor'e; It'is preferred that these solution. Drylime-sulphur compositions are also polymeric organic polysulfldes bepr'esent an used but are not as'widelyused as the solutions. aqueousdispersion or latexelike quality having The term lime sulphurfl .isemployed to include a particle size 'of'the polymericorganic polysulallthe products .01 the reactionof calcium hyrules of about l'fto'lomicrons and, having the droxide with sulphur. Whensulphurorlime-sulproperty {f iqrq picl 'translucentf D i mpl yed in spraycompositions, it is b m o m r mmsflqn for we usually the practice to addan adhesive or sticking tenacity of the 'spray 'deposit 'olthesepolymeric agent to the dust or spray composition to prevent organic'polysulfldes and the "rubber-like prop I the sulphur or limesulphurfrom "being w h erties' or the olymer areconjoined; 1 q OH or leachedfrom the treated plants by the ac- The elastic properties of thesepolymers, are tion of rainfall., .Some wetting and spreadingvregulated'jbothfbyitliefnilmber ofatioms in the agents such as milkproducts, flour, gelatin, blood rgfinic r d whi hhgg d mphflrsto.sulphuralbumen, bentonite axid otherv claysh ave found some use as stickingagents. While some oils and ke W aid pgamradialg Acofdlngly t especiallyfish oils have: been found to be the. most larger the um b ne m tom p timportant or theadhe iv s. or ot er n ect sv mg the sulphur'groupswithin the moleculesrthe andZl n icidesii h YLTQQ il be f D YBt w I morerubber-like are the properties of the D0 9? sulphur andlime-sulphunfiForges reported me'r; 'Also the greater-"thenumber jof sulphur" t e ure.the use" a spraycomm itm atoms linked to) the organic radicals; the morecontainingarijoil' and; L p and an oil on plant's resultsin considerablem polymeric material age to the plant toliageQNot o'niy. .ca'nf such. f;-s* combinations oijoiland'sulphur or oil'fandlihre .1 a a 1 H 1.- vsulphurjnot'beusedwithout serious. foliagein .l 'y.\b it; SlflDhutlfin'slllfide jcontaining,'spiayii is a powdery material, while cannotfollow orfbefollowedjby'a sp y composi v tionjcontainhigfanfoilunless atime M y al oi at least two weeks haselapsed.

I ha ve dlia'; a

are rubber-like polymers." v

The preferred polymeric. organic polysulfides ;:'can be preparedas latexlike aqueous dispersions i .v v by the methods'disclosedinmycopendingappliof Slflph ?:,.QI:,g mQ-$ lmh 1w qm eas gl i cations, Serial No.599,316, filed June 13, 1945, sy is ic ff ct of thi n w cl f pray ad nowPatent No. 2'-,'470;115', sesame; 599,317, filed juvantsrgvThesernew.spray;compositions-arecom 65 June 13, 1945, now Patent -No.2,470,529, and in venientlyandtreadily;prepared by merely- U. S. PatentNo. 2,102,564,. 1

linkage, and by the of sulphur atoms phur for nine-smphur i rubberybecomes the polymer. For examplepthe' 3 Essentially. the polymericorganic polysulfldes with which my invention is concerned are preparedby condensing a water-soluble polysulflde such as sodium, potassium orcalcium polysulnde having from 2 to 5 or more sulphur atoms per moleculewith such organic compounds as .iormaldehyde or those which have thegraphical skeleton structural i'ormula:

lat-t4 represents two adjacent carbon atoms or x-d LX l Jul;-

represents two carbon atoms separated by and where where Joined to anintervening organic structure and used provided that the substituentsare in thenature of X and X. The X and X constituents, which are splitof! by reacting with the cation of the water-soluble polysulfldereactant can be halogen, acid-sulphate, nitrate, acid phosphate,bicarbonate, formate, acetate. propionate, laurate, oleate and others.

More specifically, the organic compounds which can be employed asreactants to form the polymeric organic polysulfide condensationproducts are for example ethylene dichloride and dibromide, propylenedichloride and dibromide, the dichlorides and dibromides of unsaturatedhydrocarbon gases derived from pressure-cracking processes and naturalgas-cracking processes, the reaction products of these unsaturatedhydrocarbon gases with sulphur dichloride, as well as such disubstitutedcompounds of which the following are examples and where X and K have thesame significance as hereinbetore described:

CHsCHO CEC A,A'-dimbstitnted ethyl e B.B'-dimbstitnted ethyl etherXCHsOCHaX' 4 Dilubltltuted methyl ether XCaHsOCzHsOCaHsX' Disnbstitutedethoxy ethyl ether XCHaSCHzX' Disubltituted thiomeflul other CH:XOHsOOHaIOHaOOBaX' H; Dilubltituted LB-dimsflion 2,2-dimethyl propaneXCbHsOCHzOCaHtX' Disubetituted diethyl formal XCaHiO O CiHlX'Disubstltuted para diethoxy XCHzOCHzCHOCH:

Disubstituted dimethoxy ethane XCIHiO G 0 0134K Disubstituted diethylcarbonate 0 0 XCHJ O (ll-E103 CHgX' Disubstituted glycol dlacetatep,p'-Disubstitnted diphenyl ether p,p'-Disubstituted dibenzyl etherXC2H4SO2C2H4X' Disubstituted diethyl sulfone C|H|CHO CHCiHlA,A'-disubatituted propyl ether P.p-Disubatituted benzene xcmOcmrxclncclminclm Disubstituted para hexyl benzene Disubstituted 3-tolylpropene-2 and others as well as compounds have more than two reactivesubstituents such as 1,1,2-trlchlor.

ethane, 1,2,4-trichlor butane, l,2,3,4-tetrachlor butane, trichlormesitylene, and 2,2-bis-(parachlorophenyl) 1,1,1-trichloroethane.

The stable latex-like aqueous dispersion having the preferredcharacteristics hereinbetore described can be prepared by carrying outthe condensation reaction in the presence of an aqueous solution of asalt stable emulsifying or dispersing agent. Compounds which aresuitable emulsifying or dispersing agents are lignin sulfonates. alkylbenzene sulfonates having more than 20 carbon atoms in the alkyl group,aralkyl suli'onates, sorbitan monolaurates especially those which areoil soluble and slightly water-soluble. casein and others. From both theeconomical and technical standpoints, it has been found that the ligninsulfonates, especially the sodium. potassium and calcium llgninsulfonates are the most satisfactory emulsifying or dispersing agentsfor the preparation of the previously described aqueous dispersions ofpolymeric organic polysuliides.

The following preparations of aqueous dispersions of specific polymericorganic polysulfldes are'given to illustrate thepreparation of thepreierred aqueous": dispersions," useful according to: w.

my inventions: The'otheriorganic reactants here-x inbe'fore enumeratedcan .be employed in a like maniier to form "suitablespray; adjuvantspThe parts reported in the examples are by weight.

amixture of an aqueous solution containing 110 parts of (NI-10284.5andsix parts of lignmfsulfonate as a dispersing agent, there was'addedslowlywith vigorous stirring 70 phur'withca small amount of a"wetting'agent can-be mixed with thepaqueousdispersions ofgthe polymeric.organic. polysulfldes withyequal suc-u :tremely compatible withthe'aqueousdispersions parts of formalin (37%) while maintaining thereaction temperature at about 30 C. by external cooling. After theaddition of the formalin solu tion had been completed, the agitation wascontlnued for aboutoneliour while the temperature of the reactionmixture wasmaintained at about 30f C. Theresultingaqueous dispersion ofpoly methylene poly'suliide after being cooled to about room"temperature, was "ready 'for use; The

persion .hada Particle size of about 1 to 4. mi-

crons, butlwouldj s'e ttle readily. The polyethylene polysulilde formedwas washed three times by dec'antation to remove the" sodiuinvchlorideformedas a b'y-productduring the'condensation. The washed polyethylenepolysulfide dispersed readilyto astable latex-like dispersion.

'I'o a mixture of .480 .parts of a2tmolaraqueous solution of HMS and sixparts of sodium lignin sulfonate there was .slowly .added with. vigorousstirring 110 parts of B,B'- dichlorethyl ether while maintaining thereaction temperature at about65 C. by external "cooling; After theaddition of the chlorinated ether had been completed,

the agitation wascontinued for about one hour while thetemperatirrelofthe reaction mixture was maintained at aboutfiil'to 65?C. ,The result! ing aqueous dispersion or the polymeric organicpolysulfide thus, prepared had an average particle size of. about to 4microns. The condensation productwas washed by decantation to remove thesodium'ohloride formed during the conden-" sation processas in Examplefi'lhe washed a t q is r b, thin. layerand. llbwedft s e s d v n with; er' nai thepresence ofg' at o theft m f r elemen l mhur' w arecommonly'used intheiields of agriculture eprepared latex-like aqueous amicroscopic, translucent, ery film-when spread outin a" ,dry and couldnot be. emelyj vigorous ,rub-

phur prepared either asfl a hydrophilic sci or as a. hydrophobiesohasdescribedin the literature.

washedlflotation' sulphur, which isa by-product ofgthe manufacture offuel-{gas from coal, and

wetta-ble! sulphurs, which :are mixtures ;of sulcess. Also, lime-sulphurand other ,alkali and alkaline earth sulfides and polysulflde areexofthe polymericmaterials described above.

In the following descriptions. the elemental sulphur compositionswere'zprepared by first dispersing'the sulphur inowater byplacingtheSill-5f phur in--a container such as alive-gallon milk can and sprayingpressurized water into thecontainer with a spray nozzle, then adding the.dispersed sulphur tothe aqueous dispersion of the polymeric organicpolysulflde, and=then diluting.

r the resulting mixture tothe desired volume. The

lime-sulphur. spray compositions were "prepared by adding a suflicientvolume of an aqueous limesulphur solution having .aspecific gravity ofabout 1.283 (32 B.) to the aqueous solution of "the polymericorganicpolysulflde solution and diluting the resulting mixture to the desiredvolume. In actual field tests insecticides were added to some of thespray compositlons toaccomplish a two-fold purpose with one sprayapplication.

3, Thus, when the lime-sulphur sprays were applied lead arsenate wasadded for insecticidal activity and hydrated lime was added as acorrective for the lead arsenate. The combination of limesulphur withlead arsenate and hydratedlime is a mixture commonly usedforhortlcultural sprays.

was applied to: determine compatibility and bi'-- The following examplesillustrate the use of-the specific compositions.

A 15-year old Beauty, McIntosh, Red Delicious and Golden Delicious, wasselected-for'field tests. Since the trees had become heavily infectedwith scab. Venturia inaequalz's (Cke) Wint., during the previous year,sources of primaryinooulum were excellent. The sprays were applied witha spray unit equippedwith a single spray gun at350 to 400 poundspressure. Sevensprayswereapplied at approximately two-week intervalsfrom April .8

to J uly 4. Three trees of each variety, twelve individuals, were usedfor each treatment. To secure maximum protection with sulphur alone asulphur spray of high concentration, 10 lbs. per 'gal.;of water wasemployed. The results of the use of this sulphur spray was used as astandard for comparison. Polyethylene polysulflde as prepared in ExampleII at 2 lbs. of solids in com bination with sulfur at 10 lbs. per 100gali 'of water ological activity of this composition.

Temperature and moisture conditions were ideal for infection throughoutmost of the spraying seasonand the unsprayed trees of the moresusceptiblevarieties, Rome Beauty and McIntosh were beginningflto"defoliate 'jbythe middlefoi June. l Weather Was'cooland rain fell atintervals of about? hours throughout May. une and ,July.

- inland'for Julyii,83 in. Lesion counts on foliage were usedasthe'index'of control ofapple scab.

Tenbranches at thesamelevel around the tree were selected at random oneach "ofthe three trees'foreach variety and theratio' of infected appleorchard, three in size, which contained four varieties of apples: RomePrecipitation for May was 7.9; 'in.,' for June 5.62

clean leaves recorded. This involved the counting of about 1500 leavesfor each variety for each treatment. On the 25th of June when readingswere taken, unsprayed trees were badly damaged by the scab fungus. Thefoliage had assumed the suede-finish characteristic of systematicinfection of leaves at the periphery of the tree and had begun toabscise.

Degree of control by the sprays applied for the three most susceptiblevarieties is indicated in Table 1. Sulphur at a much higherconcentration than normally used failed to protect. This was due torapid removal of spray deposits by rain. The results of the use of thepolyethylene polysulfide and sulphur indicate almost perfect protectionin that the little infection present consisted chiefly of thatdeveloping on unprotected new growth formed in the intervals betweenspraying. None of the trees of any of the varieties sprayed with thecomposition of my invention displayed any evidence ofdamage. Color offoliage of these trees was excellent.

The degree of scab control on the fruit under slightly differenttreatment in another section of the orchard is indicated below in Table2 for the varieties Red Delicious and McIntosh. The spray compositionswere prepared and applied as described above. The percentage infectedfruit is given for mature fruit.

TABLE 2 Variety M clntosh Average Po Cent Treatment Infected F I-nitControl (Unsprayed) Substantially 100.

8 lbs. Wettable Sulphur/100 gal 34.

1 lb. dispersion of Ex. II and 3 lbs. wettable sul- 29.

phur/100 gal.

Variety Red Delicious Average Treatment fi gg Fruit Control (Unsprayed)100 Flotation SulFhur Pasta 1 l2, l and 8 lbs. per 100 gallons. 22 4lbs. dispers on of Ex. II and Flotation Sulphur Pasta 1 l2, l0 and 8lbs. per 100 gallons 4. 0

1 Variable dosages of flotation sulphur paste (45% snl bur) representprebloom, bloom and first cover dosages respective y.

Additional evidence of this resistance to weathering of spray depositsis illustrated in Table 3 by the sulphur values for the leaves'six weeksafter the last spray composition had been applied. During this six weeksthe deposit was subjected to 9.7 inches of intermittent rainfall. Matureleaves of comparable age were collected from McIntosh trees and the areaof the leaves was determined by a planimeter from the outline of theleaves traced on paper. 25 leaves were obtained from the trees of eachexperi- '8- mental group. The leaves were. dried and the sulphur contentascertained by the method of Parks et al. as reported in Industrial andEn-' gineering Chemistry, Analytical Edition, 15: 527- 533, 1943.

The high sulphur values for apple leaves sprayed with the polyethylenepolysulfide sulphur composition relative to that of leaves sprayed withsulphur are convincing evidence of the tenacity and resistance toweathering of spray deposits containing this polymeric organicpolysulflde. Analysis also shows that the polymer is an excellentadhesive for sulphur.

EXAMPLE V In an adjoining commercial orchard of several acres of matureBaldwin and McIntosh trees, dusting with sulphur was practiced for thecontrol of scab. Rapid removal of sulphur by the frequent rains the lastweek of April and the first week of May combined with ideal conditionsfor spore germination resulted in a heavy infection of foliage. On May6. polyethylene pentasulflde at 1 lb. of solids with lime-sulphur at 1gal. of commercially available 32 B. solution and with arsenical, 5 lbs.lime and 5 lbs. lead arsenate, per gal. of water was applied to destroy,or burn-out, infected areas of tissue (scab lesions) The scab waseradicated without apparent injury to the foliage. Two gallons ofcommercially available lime-sulphur per 100 gallons of water. which isnormally used for burning out" scab lesions endangers the foliage. Laterin the season, June 5, polyethylene pentasulflde was again used withlime-sulphur of the same concentration in a mixed insecticidal spray ofnicotine sulfate and arsenicals for the eradication of scab in anotherunit of the same orchard. Here. too. the lesions were destroyed withoutapparent injury to the foliage.

The aqueous dispersions described in Examples I and III have also beenemployed in preparing similar spray compositions and gave results equalto those described above. In fact, any of the hereinbefore describedaqueous dispersions of polymeric organic polysulflde may be used ifdesired.

The above specific concentrations of the toxioants can be varied to suitthe purposes and conditions for which they are to be used. In general,the sulphur concentrations employed for horticultural spray purposes,varies from about one pound of sulphur, dry basis, to about 6 pounds per100 gallons of spray while the concentrations of lime-sulphur vary fromabout 2 to about 5 pounds, on a dry basis, per 100 gallons of spray. Butfor unusual conditions of heavy infestation of certain insects andfungus diseases, the sulphur concentration will be 10 pounds or more per100 gallons of spray and the lime-sulphur concentration will be as highas 25 pounds. on a dry basis, per 100 gallons to control heavyinfestations of leaf curl" on peach trees. For any of the concentrationsof sulphur and the usual concentrations of lime-sulphur. it is neces- 9sary to use only about one pound to about pounds of an aqueous,dispersion of a polymeric organic polysulfide containing 50% of thepolysulflde by weight, but for the higher concentrations of lime-sulphur6 to 10 pounds of the 50% This application is a continuation-in-part ofmy copending application Serial No. 599,316, filed June 13, 1945, nowPatent No. 2,470,115.

I claim:

1. A composition comprising a stable dispersion of one to five parts byweight of particles of polyethylene polysulfide of a size no greaterthan 10 microns in diameter dispersed in an aqueous solution of a ligninsulfonate, said polysulfide containing 3 to 5 sulfur atoms per molecularunit,

. and also'comprising from 1 to 20 parts by weight of separate particlesof a material'selected from the class consisting of sulfur and limesulfur.

2. A composition comprising 1 to 10 parts by weight of particles ofelemental nulfur and 1 to 5 parts by weight of separate particles ofpolyethylene polysulflde of a size no greater than 1 to 3 microns indiameter dispersed in an aqueous solution of a lignin sulfonate, saidpolysulfide containing 3 to 5 sulfur atoms per molecular unit.

3. A composition comprising 1 to 20 parts by weight of lime-sulfur and 1to 5 parts by weignt of separate particles of polyethylene polysulfideof a size no greater than 1 to 3 microns in diameter dispersed in anaqueous solution of' a lignin sulfonate, said polysulflde containing 3to 5 sulfur atoms per molecular unit.

WILLIAM D. STEWART.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,043,941 Williams June 9. 19362,102,564 Bonstein Dec. "14, 1937 2,142,145 Patrick Jan. 3, 1939 OTHERREFERENCES Martin: The Principles of Plant Protection," 2a Ed. (1036),pages 102-104, 109, 113-119. (Copy in Div. 43.)

1. A COMPOSITION COMPRISING A STABLE DISPERSION OF ONE TO FIVE PARTS BYWEIGHT OF PARTICLES OF POLYETHYLENE POLYSULFIDE OF A SIZE NO GREATERTHAN 10 MICRONS IN DIAMETER DISPERSED IN AN AQUEOUS SOLUTION OF A LIGNINSULFONATE, SAID POLYSULFIDE CONTAINING 3 TO 5 SULFUR ATOMS PER MOLECULARUNIT, AND ALSO COMPRISING FROM 1 TO 20 PARTS BY WEIGHT OF SEPARATEPARTICLES OF A MATERIAL SELECTED FROM THE CLASS CONSISTING OF SULFUR ANDLIME SULFUR.